Use of hydrocarbon polymers to improve oil-containing waxes

ABSTRACT

This invention relates to the use of hydrocarbon polymers for example of the type described in U.S. Pat. No. 4,060,569 to bind oil contained in waxes so that, in end use performance, the wax more closely equals fully refined wax. Among other things, the hydrocarbon polymer not only inhibits and/or prevents the oil in the wax from &#34;sweating&#34; or exuding to the surface but also hardens the wax. The hydrocarbon polymers can also be used to thicken oil to a paste or gel.

A world wide shortage of high grade waxes exists. For example, atpresent there is an extreme shortage of high grade paraffin waxes, whichnecessitates allocation. Thus, although there is a plentiful supply ofsoft hydrocarbon waxes such as soft paraffins, there is an acuteshortage of hard paraffin waxes.

Although the addition of polymers such as polyethylenes to waxesincreased their hardness, the presence of polyethylene in waxundesirably increases:

(1) the viscosity, and

(2) the cloud point of the blend.

In Ser. No. 926,763 filed July 21, 1978 the hydrocarbon polymers of U.S.Pat. No. 4,060,569 are blended into waxes such as natural waxes,hydrocarbon waxes etc., such as paraffin, etc., to obtain waxes whichare characterized by improved hardness. The hardness of the blend isunexpectedly greater than the hardness of each component. In additionthe blending of hydrocarbon polymers in waxes has a lesser effect on theundesirable properties of

(1) increased viscosities and

(2) increased cloud points that occur when polyethylenes are blendedinto wax.

For example, in Ser. No. 926,763, if one were to take a paraffin with apenetration of 12 and blend it with 1:1 with the hydrocarbon polymerwith a penetration of 6, the resulting blend has a penetration as low as2. Thus, one obtains an unusual product, one that is very hard, yet isrelatively low melting, and has a relatively low viscosity and arelatively low cloud point. Hardness is measured by the needlepenetration test ASTM D-1321, a standard for the petroleum wax industry.

Paraffin waxes are classified as slack wax, semi-refined, and fullyrefined. The U.S. Bureau of Mines classifies slack waxes andsemi-refined waxes under one classification "Other Crystalline."Paraffin waxes having oil contents of 0.5% maximum are classified asfully refined paraffins. In 1969 fully refined paraffin constituted 45percent of the total U.S. wax production as reported by the Bureau ofMines and in 1976 it still was at the same 45 percent level. "Othercrystalline" paraffins have increased from 35 percent in 1969 to 42percent in 1976. In recent years the increased demand has been on fullyrefined paraffin waxes resulting in shortage and allocations by manyparaffin producers. Thus, there is a need for a synthetic additive thatwill harden the paraffin and bind the oil so that the end useperformance of an oily paraffin can more closely equal fully refinedparaffins.

We have now discovered that the performance of the hydrocarbon polymersof U.S. Pat. No. 4,060,569 is not limited to use with low oil contentwaxes such as natural waxes, hydrocarbon waxes, etc., such as paraffinwaxes, etc., to obtain waxes which are demonstrably improved in hardnessas described in Ser. No. 926,763 filed July 21, 1978, but can beexpanded to include oil-containing waxes. We have found that when thehydrocarbon polymers of U.S. Pat. No. 4,060,569 are blended intooil-containing waxes such as natural waxes, hydrocarbon waxes, etc.,such as paraffin waxes, etc., one obtains a hard wax of improvedproperties by binding the oil in the wax and hardening it so that thewax in end-use performance more closely equals fully refined wax. Theuse of hydrocarbon polymers not only inhibits and/or prevents the oil inthe wax from "sweating" or exuding to the surface but also hardens thewax.

Further, a wide variety of oils can be thickened or hardened to pastesor gels with the hydrocarbon polymers of the invention. Examples of oilsinclude vegetable oils, both drying and non-drying; petroleum or mineraloils of various classes including those of open-chain hydrocarbons,cyclic hydrocarbons or cycloparaffins, various oils obtained frompetroleum products such as naphthas, gas fuel, lubricating and heavieroils; coal distillates, including naphthas, creosote oils, anthraceneoils, ethereal oils, etc.; resin oils and wood distillates, includingthe distillates of turpentine, rosin spirits, pine oil and acetone oils;and animal oils.

In the past some microcrystalline waxes and more recently somepolyethylenes have been used to bind the oil in paraffins. Thesematerials are not very efficient and raise the cloud point of theparaffin. The hydrocarbon polymers of this invention are much moreefficient and do not raise the cloud point of most paraffins. The cloudpoint is defined as the temperature at which the highest meltingfractions begin to crystallize. High cloud point is an undesirableproperty for paraffin waxes in most cases. To overcome a high cloudpoint, the application temperature must be above the cloud point andthis usually results in a number of other problems relating to theapplication temperature being too high for the material, such as, excesswax penetration in paper goods, too long cool-time and poor control ofwax weight.

The addition of hydrocarbon polymers of this invention such as at about1 to 5% level to high oil content paraffins results in an outstandingincrease in oil retention. As the percentage of hydrocarbon polymers isincreased above the 5% level, the increase in change begins to levelout, but the hydrocarbon polymers can be used at any of the higherpercentage levels.

These hydrocarbon polymers have excellent oil binding properties. Theseproperties can be utilized to bind excess oil in paraffins. A paraffinwax with an oil content of 0.5% or more is considered to have a high oilcontent. When the oil is tied-up, the high oil content paraffin waxbecomes a much more useful material which can be used in manyapplications where a fully refined paraffin is normally used. The reasonoily paraffins can not be used in many applications is because the oil"sweats" or exudes from the paraffin, which results in an oily "feel" tothe paraffin and may stain anything that comes in contact with theparaffin. In some paraffins with high oil content, free oil can beobserved on the surface of the wax. With the hydrocarbon polymers ofthis invention, a wide variety of oils, as above exemplified, can bemade into pastes or gels. The amount of hydrocarbon polymer added to oilwill determine the consistency of the product.

The weight percentage of hydrocarbon polymer employed in the blend inthe wax to inhibit exudation of oil will vary depending on many factorssuch as the particular wax, the particular hydrocarbon polymer, thehardness desired, etc. In general, as the percentage of hydrocarbonpolymer in the wax increases, hardness also increases. Thus, one canemploy about 0.5% or more by weight of hydrocarbon polymer such as fromabout 1 to 5% or more, such as from 5-50%, but preferably from about 1to 10, with an optimum of about 5%.

Any suitable wax or wax-like material may be hardened according to thisinvention. These include petroleum waxes such as paraffin wax,microcrystalline wax, etc., natural waxes such as beeswax, carnauba,candellila, montan, peat wax, ouricury wax, esparto wax, rice wax, sugarcane wax, maize wax, etc., synthetic waxes such as amide waxes, esterwaxes, etc., or any wax-like material which can be upgraded in accordwith this invention. The only requirements are that the hydrocarbonpolymer be compatible with the wax or wax-like material and capable ofbeing upgraded in accord with this invention.

The hydrocarbon polymers employed in this invention are described andclaimed in Ser. No. 644,138 filed Dec. 24, 1975, now U.S. Pat. No.4,060,569 issued Nov. 29, 1977. This patent relates to hydrocarbonpolymers having lower penetration or greater hardness (H), greaterviscosities (V), higher molecular weights (MW), but having meltingpoints (MP) and congealing points (CP) which are essentially no higher,but preferably lower than the original hydrocarbon,

i.e., hydrocarbon Polymer's MW, V, H> original hydrocarbon

hydrocarbon Polymer's MP, CP< original hydrocarbon.

These polymers are prepared by polymerizing hydrocarbons under freeradical conditions at low pressures.

The polymers are unique in that although hydrocarbon polymers generallyhave higher molecular weight, greater viscosity and greater hardnessthan the starting hydrocarbon they generally have higher melting pointsand congealing points than the starting hydrocarbons.

Hydrocarbons employed are primarily alpha olefins of the formula RCH═CH₂but also include alpha olefins of the vinylidene structure ##STR1## or amixture of alpha olefins, vinylidenes, internal olefins and saturates.Because alpha olefins are primarily employed, this term is often used toindicate both alpha olefins and mixtures of various combinations ofalpha olefins, vinylidenes, internal olefins and saturates.

U.S. Pat. No. 4,060,569 describes and claims alpha olefins which can bepolymerized or copolymerized in the presence of free radicals at lowpressures to yield polymers of increased molecular weight, higherviscosities, and greater hardness but lower melting and congealingpoints than the original alpha olefins from which they are derived.

Since low pressures are employed, less expensive equipment may be used.Since the polymers have low melting and congealing points they haveadvantages in processing applications where low melting and congealingpoints are necessary. These polymers have many uses, for example, theypossess low shrinkage and are therefore useful as casting waxes. Theyare useful in printing inks where low temperature applications areneeded. They are useful in applications where low melting and congealingpoints are desirable such as in hot melt adhesives, pour pointdepressants, carbon paper inks, coatings, etc. In addition, thesematerials can be oxidized to yield emulsifiable products which can beused in polishes, etc.

In addition, the oxidized products can be further reacted withisocyanates and/or other materials to improve their hardness and pigmentdispersant properties.

The polymers of U.S. Pat. No. 4,060,569 have high viscosity (indicatinghigh molecular weight) and low penetration. These properties are verydesirable in a polymeric wax.

The melting point, however, will be low in comparison to its molecularweight. Because of its low melting point and congealing point the waxhas processing advantages over higher melting point waxes. Thisdepressed congealing point and melting point is a unique part of thisinvention. The molecular weight and viscosity of the products of thisinvention are usually indicative of waxes that have a much highercongealing point and melting point. An example is "BARECO" Polywax 2000.For a molecular weight of 1674 the congealing point is 233° F. and themelting point is 258.5° F., in contrast to the present invention wherefor a corresponding molecular weight (Example 4), the congealing pointis 148° F. and the melting point is 165.7° F.

The melting point and the congealing point of the resulting wax isdependent upon the melting point and congealing point of the initialalpha olefin. The initial alpha olefin (or mixture of alpha olefins) inthis invention is a solid at room temperature. The melting point and thecongealing point of the final product is essentially no higher than themelting point and the congealing point of the initial alpha olefin.However, the viscosity and the hardness of the resulting wax are muchgreater than that of the original alpha olefin. The melting point andthe congealing point of the initial alpha olefin can be adjusted byusing blends of low melting point alpha olefins and high melting pointalpha olefins.

The products of U.S. Pat. No. 4,060,569 have outstanding oil retentionproperties. They are very easy to dissolve in a number of solvents. Thewaxes also exhibit very low shrinkage because of the low degree ofcrystallinity that is apparent from their low density. Except forimpurities present in the starting materials the product is homogeneousin nature, i.e., it is not merely a blend of a high molecular weight andhard material with a low molecular weight and soft material. If theproduct were merely a blend, then fractionation by a suitable solventwould reveal this. However, fractionation by a suitable solvent yieldedtwo fractions; the lower melting point material appeared to compriseimpurities present in the starting materials such as unreacted saturatesand similar products while the harder material had physical propertiessimilar to the overall product. This is illustrated in Example 19.

The properties of the final product of U.S. Pat. No. 4,060,569 can bealtered in four ways: (1) starting material, (2) concentration ofperoxide, (3) length of reaction time, and (4) reaction temperature. Themelting point and congealing point of the final product is based on theinitial material. The melting point and congealing point of the initialmaterial are the upper limits for the final material. The peroxideconcentration affects the final properties chiefly in three ways: (1)molecular weight and viscosity, (2) hardness, and (3) congealing andmelting points. By using more peroxide the viscosity increases,indicating an increase in molecular weight with an increase in hardnessand a decrease in melting and congealing points. If excess peroxide isused, the reaction tends to become unstable and a crosslinked gell mayform. Temperature of reaction and time of reaction are interrelated asfar as they affect the properties of the final product. The preferredtemperature and time of reaction should be sufficient for the catalystto go through eight half-lives. After eight half-lives the concentrationof peroxide is approximately 4/10 of 1% the original concentration. Fora reaction time less than eight half-lives of the peroxide the catalysthas not been economically used. After eight half-lives the reaction isslow. The reaction could be carried on for a longer period of time or ashorter period of time. The eight half-lives is a convenient time to useeconomically.

Hardness is also affected by the initial raw material. If the olefinsused are branched then the resulting material will be branched and thepenetration will not be as low as where the initial materials arelinear. By using linear raw materials the melting point and congealingpoint are higher than if branched olefins are used. The molecular weightof the initial material is also important. Using a low molecular weightbranched starting material, the resulting melting point, congealingpoint, and hardness will be lower than if the original material waslinear and had a high molecular weight.

The selection of the peroxide catalyst is dependent on many factors:cost, decomposition products, and the decomposition temperature. Thepreferred peroxide catalyst is di-t-butyl peroxide. The reason for thisis its low cost, its decomposition temperatures, and the ease in whichits decomposition products (t-butyl alcohol and acetone) can be removedfrom the resulting wax.

The reaction procedure is dependent upon which catalyst is used. Whenusing di-t-butyl peroxide the catalyst must either be added to theinitial charge material while it is at a temperature below 110° C. orthe peroxide must be added under pressure. When using di-t-butylperoxide the reaction is run under nitrogen pressure of at least 20 psi.This maintains the peroxide in the liquid wax. After the proper reactiontime, the wax is then vacuum stripped to remove the decompositionproducts. Failure to remove decomposition products can lead toundesirable effects on the melting point, congealing point, penetrationand flash.

The molecular weights of the product of this invention can vary widely.By way of illustration, they can vary from at least about 300, such asfrom about 300 to 6000 or more, for example from about 650 to 5000, butpreferably from about 750 to 3000. The molecular weight will depend uponthe amount of peroxide, the temperature of the reaction, the time of thereaction, and the starting materials.

Many polymerizations are done in a solution. However, thispolymerization is generally carried out in bulk. The advantage of thisis that separation of the wax from the solvent is avoided. However, theproducts of this invention can also be produced by solutionpolymerization if desired.

The alpha olefins employed in this invention are of the followingidealized formula

    RCH=CH.sub.2

where R is alkyl, for example, having about 4 to 50 or more carbons.These include monomers such as 1-hexene, 1-octene, 1-decene, 3-methyldecene-1, 1-tetradecene, etc. They may be linear or branched.

Also included within the term alpha olefin are those which are preparedby polymerizing olefins such as ethylene in the presence of Ziegler typecatalysts.

Illustrative of these types of alpha olefins are those sold by Gulf, forexample:

(1) Gulf Alpha Olefin Fraction C₂₀ -C₂₄ which contains the followingtypical carbon distribution:

    ______________________________________                                               C.sub.18      1 wgt. %                                                        C.sub.20     49                                                               C.sub.22     42                                                               C.sub.24      8                                                               C.sub.26      0.1                                                      ______________________________________                                    

(2) Gulf Alpha Olefin Fraction C₂₄ -C₂₈ which contains the followingtypical carbon distribution:

    ______________________________________                                               C.sub.22     0.3 wgt. %                                                       C.sub.24    28                                                                C.sub.26    44                                                                C.sub.28    20                                                                C.sub.30 +   8                                                         ______________________________________                                    

(3) Gulf Alpha Olefin Fraction C₃₀ + which contains the followingtypical distribution: T,0141

                                      TABLE 1                                     __________________________________________________________________________    Chevron Chemical Co.                                                          CARBON RANGE                                                                                C.sub.6 -C.sub.9                                                                   C.sub.10                                                                          C.sub.11 -C.sub.14                                                                 C.sub.15 -C.sub.18                                                                 C.sub.18 -C.sub.20                                                                   C.sub.15 -C.sub.20                    __________________________________________________________________________    Straight Chain Mono                                                           Alpha Olefins, Wg. %                                                                        89   90  89   91   86     88                                     Diolefins, Wt. %                                                                           4    5   6    8    4      5                                      Paraffins, Wt. %                                                                           3    2   1    2    9      5                                     Appearance    Clear and bright and free of sediment                           Color, Saybolt                                                                              +18  +17 +14  +7   <-16   -12                                   Density (20°/4° C.) g/ml                                                      0.713                                                                              0.751                                                                             0.770                                                                              0.783                                                                              0.797  0.787                                 Density (60°/60° F.) lb/gal                                                   5.95 6.27                                                                              6.42 6.57 6.68   6.60                                  Flash Point, TOC, °F.                                                                <30  103 162  260  330    280                                   Pour Point, °F.                                                                      -    -   -20  +40  +70    +55                                   Bromine No. g/100g                                                                          165  118 98   73   57     67                                    Water Content, ppm                                                                          130  130 130  80   40     50                                    Sulfur content, ppm                                                                         5    8   10   15   15     15                                    Carbon Number                                                                 Distribution, Wt. %                                                           C.sub.5       2                                                               C.sub.6       39                                                              C.sub.7       24                                                              C.sub.8       17                                                              C.sub.9       16   4                                                          C.sub.10      2    95  1                                                      C.sub.11           1   27                                                     C.sub.12               24                                                     C.sub.13               24                                                     C.sub.14               23   1           1                                     C.sub.15               1    29          17                                    C.sub.16                    28          18                                    C.sub.17                    27   1      17                                    C.sub.18                    1    37     15                                    C.sub.19                    1    37     15                                    C.sub.20                         30     12                                    C.sub.21                         9      3                                     Average Molecular Weight                                                                    100  140 174  228  269    244                                   __________________________________________________________________________

Other alpha olefins can also be employed individually, in combination,or as components of commercial raw materials.

The term alpha olefin as employed herein relates primarily to alphaolefins of the formula RCH═CH₂ but does not exclude alpha olefins of thevinylidene structure ##STR2## or a mixture of alpha olefins,vinylidenes, internal olefins and saturates.

Any suitable free radical catalyst can be employed. Thus, any compoundcapable of forming free radicals can be employed. In practice, the mostconvenient free radical forming compounds are peroxides andhydroperoxides and a wide variety of those compounds can be employed.

Peroxides and hydroperoxides are illustrated by the general formula

    ROOR', ROOH

where R and R', which may be the same or different, are hydrocarbon orsubstituted hydrocarbon groups, for example, alkyl, aryl, cycloalkyl,aralkyl, alkaryl, heterocyclic, etc.

Any suitable amount of peroxides can be employed provided it is capableof acting as a catalyst in the reaction. In practice a molar ratio of atleast about 0.005 of peroxide to alpha olefin is employed, such as fromabout 0.01-0.35 or more, for example from 0.02-0.35, such as from about0.025-0.32, but preferably from about 0.04 to 0.30.

A convenient measure of the effective presence of peroxide is itshalf-life which is conveniently employed as a measure of reaction timebased on the number of half-lives.

In general, reaction time is from about 1 to 20 or more half-lives, suchas from about 3 to 15 half-lives, for example, from about 4 to 12half-lives, but preferably from about 5 to 10 half-lives.

Although most polymerizations using peroxides to prepare thermoplasticpolymers are carried out at high pressure, the present polymerizationsare carried out at low pressures. The only pressure that is needed isthat to insure that the peroxide or one of the alpha olefins does notvaporize from the reaction. In certain instances, such as in Example 15,no pressure was needed.

A wide variety of peroxides can be employed. Nonlimiting examples are:di-t-butyl peroxide, t-butyl perbenzoate, t-butyl peracetate, benzoylperoxide, and t-butyl peroctoate. The temperature at which this reactionis carried out is dependent upon the peroxide used. With a peroxide thathas a low decomposition temperature (like t-butyl peroctoate) then thetemperature of the reaction can be low. However, for a peroxide that hasa high decomposition point (such as di-t-butyl peroxide) then thereaction temperature will be higher. The temperature of the reaction isnormally set such that the peroxide would have a half-life betweenone-half hour and three hours. This, however, does not exclude usinghigher temperatures or lower temperatures. Another factor in determiningthe temperature of the reaction is reactor control and economics. If ahigher temperature is used then the reaction time will be shorter;however, the control of the process will be more difficult. By using alower reaction temperature the process is very easy to control but thelonger reaction time is an economic disadvantage and undesirable.

In carrying out the process, the alpha olefin and a peroxide are reactedat a temperature sufficiently high to promote free radical formation.Since heat promotes free radical formation, a temperature sufficientlyhigh to promote the decomposition of the peroxide, without causingdecomposition of reactants and products, is employed. Depending on theperoxide, temperatures of about 40°-250° C., such as about 80° to 200°C., for example about 100° to 180° C., but preferably about 130° to 165°C., are employed. The temperature should be sufficiently high to keepall reactants in solution or in a molten state.

In the case of di-t-butyl peroxide the best yields are obtained in theranges of about 100° to 250° C., but preferably about 130° to 165° C.

Any suitable free-radical producing agent capable of forming reactivesites can be employed. These include peroxides, hydroperoxides, etc.,for example benzoyl peroxide, acetyl peroxide, 2,4-dichlorobenzoylperoxide, di-t-butyl peroxide, tert-butyl hydroperoxide, methyl benzylhydroperoxide, cumene hydroperoxide, peracetic acid, tert-butylpermaleicacid, lauryl peroxide, methyl ethyl ketone peroxide, dicumyl peroxide,di-tert-butyl diperphthalate, tert-butyl peracetate, and the like.

Other sources of free radicals besides peroxides can also be employed,for example high energy ionizing irradiation, etc., cobalt inconjunction with hydroperoxides, inorganic peroxy compounds such aspersulfates, hydrogen peroxide, etc., azo compounds of the generalformula R--N═N--R such as azobenzene, azomethane,azobisisobutyronitrile, etc., acyl-aryl nitrosoamides such asnitrosoanilide, etc.

The following examples are presented for purposes of illustration andnot of limitation.

EXAMPLE 1

Typical properties of Gulf C₃₀ + Alpha Olefin which is used as astarting material in many examples are shown below as illustrative of astarting material and to list the tests that are used in evaluation. Itsproperties are presented in the following Table Example 1.

    ______________________________________                                        Flash (ASTM D-92) (°F.)                                                                          500                                                 Vis. @ 210° F. (SUS) (ASTM D-88)                                                                 61                                                  Vis. @ 300° F. (SUS) (ASTM D-88)                                                                 42                                                  Color (Saybolt) D-156     2.0                                                 C.P. (ASTM D-938) (°F.)                                                                          160                                                 M.P. (ASTM D-127) (°F.)                                                                          174.5                                               Pen. @ 77° F. (.1MM) (ASTM D-1321)                                                               14                                                  Pen. @ 110° F. (.1MM) (ASTM D-1321)                                                              48                                                  Pen. @ 140° F. (.1MM) (ASTM D-1321)                                                              180                                                 Acid No.                  Nil                                                 Sap. No.                  Nil                                                 Molecular Weight Vapor Pressure                                               Osmometry (VPO)           510                                                 ______________________________________                                    

Chemical Composition

1.4% Saturates

67.5% Normal Alpha Olefins

25.4% Vinylidene Olefins

5.7% Internal Olefins

EXAMPLE 2

This example is presented to show that the products of the invention arenot the result of thermally initiated reaction only. The data shownbelow is the result of holding Gulf C₃₀ + Alpha Olefin at 153° C. (307°F.) under a 100 lb. psig nitrogen pressure (to prevent oxidation of thematerial) for eight hours without peroxides. This simualtes the reactiontime of approximately 9.0 half-lives of di-t-butyl peroxide. The resultsare presented in the following Table Example 2.

    ______________________________________                                        Flash (°F.)   515                                                      Vis. @ 210° F. (SUS)                                                                        64                                                       Vis. @ 300° F. (SUS)                                                                        43                                                       Color (ASTM) 1500    0.5+                                                     C.P. (°F.)    159                                                      M.P. (°F.)    175.5                                                    Pen. @ 77° F. 11                                                       Pen. @ 110°  F.                                                                             44                                                       Acid No.             Nil                                                      Sap. No.             Nil                                                      ______________________________________                                    

EXAMPLE 3

2,000 grams of Gulf C₃₀ + Alpha Olefin was mixed with 150 grams ofdi-t-butyl peroxide (this corresponds to a molar ratio of 0.262 based onthe C₃₀ +). It was then reacted in an agitated vessel under 80 psig ofnitrogen pressure at 141° C. (286° F.) until 8.0 half-lives of theperoxide had elapsed. A sample was drained and then vacuum stripped at29 in. Hg. vacuum until bubbling stopped. Data shown below gives theproperties of the resultant material. Comparing this data with that inExample 1 shows the extent of reaction. Although the product of thisinvention is hard and viscous, the congealing point and melting point ofthe reaction product are lower than the congealing point and meltingpoint of the charge stock.

(In certain instances the melting points and congealing points of theproducts of U.S. Pat. No. 4,060,569 may be reported to be erroneouslyhigh, because high viscosities in the products may make measurementsdifficult. To avoid the difficulty, the products will be described ashaving melting and congealing points which are essentially in the rangeof the original alpha olefin or lower, depending on the accuracy ofmeasurement, the amount of impurities in the product, etc.)

This material has excellent oil retention properties, low shrinkage uponcooling and a glossy surface. The results are presented in the followingTable Example 3.

    ______________________________________                                        Flash (°F.)   570                                                      Vis. @ 300° F. (SUS)                                                                        594                                                      Color (ASTM)         0.5-                                                     C.P. (°F.)    142                                                      M.P. (° F.)   160.2                                                    Pen. @ 77° F. 4.5                                                      Pen. @ 110° F.                                                                              22                                                       ______________________________________                                    

EXAMPLE 4

2,000 grams of Gulf C₃₀ + Alpha Olefin was mixed with 100 grams ofdi-t-butyl peroxide. The amount of peroxide used corresponds to a molarratio of 0.175 based on moles of C₃₀ +. The purpose of this example isto show the effect of catalyst concentration on the resulting molecularweight and physical properties. This mixture was then reacted under 80psig of nitrogen pressure at 140° C. until 15 half-lives of peroxide hadbeen achieved. The material was then drained and the decompositionproducts of the peroxide (t-butyl alcohol and acetone) were strippedfrom the product wax. This stripping was done by subjecting the productwax to 29 in. mercury vacuum until the bubbling stopped. Resulting datais shown below. As can be seen this wax is less viscous than thatproduced in Example 3. This is the result of decreased molecular weightof this wax versus that in Example 3. An infrared spectrum of this waxshowed that there still were some vinyl and vinylidene groups remainingin the wax. However, an infrared spectrum of the wax in Example 3 showedpractically no vinyl or vinylidene groups present. This wax was alsovery hard and has excellent oil retention properties. The results arepresented in the following Table Example 4.

    ______________________________________                                        Flash (°F.)   550                                                      Vis. @ 210° F. (SUS)                                                                        470                                                      Vis. @ 300° F. (SUS)                                                                        155                                                      Color (ASTM)         0.5-                                                     C.P. (°F.)    148                                                      M.P. (°F.)    165.7                                                    Pen. @ 77° F. 5.5                                                      Pen. @ 110° F.                                                                              24                                                       ______________________________________                                    

EXAMPLE 5

2,000 grams of Gulf C₃₀ + Alpha Olefin and 25 grams of di-t-butylperoxide (molar ratio 0.0437 based on C₃₀ +) were mixed and then reactedat 152° C. (306° F.) under 100 psig nitrogen pressure in an agitatedvessel until 8.0 half-lives of the peroxide had been reached. At thispoint the sample was drained. Part of the sample was then vacuumstripped at 29 in. Hg. until the bubbling stopped. The results are shownbelow. The purpose of this example is to again show the effect ofcatalyst concentration on the final properties of the material. As canbe seen this wax is not as viscous as those in Examples 3 and 4 (has alower molecular weight), but it is a hard wax.

The results are presented in the following Table Example 5.

    ______________________________________                                        Flash (°F.)   515                                                      Vis. @ 210°  F. (SUS)                                                                       90                                                       Vis. @ 300°  F. (SUS)                                                                       65                                                       Color (ASTM)         0.5-                                                     C.P. (° F.)   154                                                      M.P. (° F.)   172.0                                                    Pen. @ 77°  F.                                                                              5.5                                                      Pen. @ 110°  F.                                                                             32.0                                                     ______________________________________                                    

EXAMPLE 6.

2,000 grams of Gulf C₃₀ + Alpha Olefin and 200 grams of di-t-butylperoxide were reacted in an agitated vessel under 80 psig nitrogenpressure at 140° C. (284° F.). After 11 half-lives of the peroxide thematerial was gelled in the reactor. It exhibited signs of being highlycrosslinked. This reaction product is highly undesirable. The gelling isa result of a combination of two factors: (1) the catalyst concentrationand (2) the reaction time. Intermediate samples were taken of thisexample. After 3.5 half-lives the material was still liquid but it ishighly viscous. The maximum amount of peroxide that is generally usedfor 8.0 half-lives reaction time at 285° F. is approximately 0.28 on amolar basis. Above that catalyst concentration the reaction time isshorter if gellation of the wax is to be prevented.

Listed below are intermediate samples taken during the above experimentthat were vacuum stripped as the other samples have been. As can beseen, reacting DTBP* at a molar ratio of 0.35 for 1.5 half-lives gives aproduct whose properties would be anticipated for a reaction betweenDTBP and Gulf C₃₀ + Alpha Olefin at a molar ratio of 0.226. (0.226 isthe equivalent amount of peroxide that became activated in 1.5half-lives (0.35×(1-(0.5)¹.5)=0.226).

    ______________________________________                                        Length of Reaction (Half-lives)                                                                    1.5       3.5                                            Flash (°F.)   540       590                                            Vis. @ 210° F. (SUS)                                                                        630       2903                                           Vis. @ 300° F. (SUS)                                                                        228       1130                                           Color (ASTM)         0.5-      0.5+                                           C.P. (°F.)    146       153                                            M.P. (°F.)    162.7     162.5                                          Pen. @ 77° F. 6.0       4.0                                            Pen. @ 110° F.                                                                              25.0      18                                             ______________________________________                                    

EXAMPLE 7

100 parts Gulf C₃₀ + Alpha Olefin and 5 parts DTBP were mixed andreacted at 296° F. in a closed, agitated vessel under 50 psig ofnitrogen. Listed below are the viscosities of samples taken at thedesignated time during the run. As can be seen, the viscosity doesincrease as time of reaction increases but at a decreasing rate. This isthe reason the reaction is normally carried on for approximately 8.0half-lives.

    ______________________________________                                        Time of Reaction (Half-lives)                                                                   Viscosity @ 300° F. (SUS)                            ______________________________________                                        3.5               99                                                          4.9               116                                                         6.6               131                                                         8.3               136                                                         12.0              148                                                         ______________________________________                                    

EXAMPLE 8

600 grams of Gulf C₃₀ + Alpha Olefin was reacted with 30 grams ofdi-t-butyl peroxide at 260°-270° F. (130° C.) until 7.5 half-lives hadbeen achieved. The sample was drained and stripped and the results arelisted below. By comparing these with those of Example 4 the effect oftemperature is noted. Lower temperatures tend to make the catalyst moreeffective (increased viscosity over Example 4).

The results are presented in the following Table Example 8.

    ______________________________________                                        Flash (°F.)   565                                                      Vis. @ 210° F. (SUS)                                                                        625                                                      Vis. @ 300° F. (SUS)                                                                        237                                                      Color (ASTM)         0.5-                                                     C.P. (°F.)    147                                                      M.P. (°F.)    166.0                                                    Pen. @ 77° F. 6.5                                                      Pen. @ 110° F.                                                                              20.0                                                     Pen. @ 140° F.                                                                              184.0                                                    ______________________________________                                    

EXAMPLE 9

100 parts of Gulf C₃₀ + Alpha Olefin was reacted with 7.5 parts ofdi-t-butyl peroxide at 300° F. until 8.0 half-lives had been achieved.At this point the sample was cooled to 270° F. and vacuum stripped. Theresults are shown below. Comparing these results with those of Example 3show that an increase in reaction temperature decreases the extent ofreaction (lower viscosity).

The results are presented in the following Table Example 9.

    ______________________________________                                        Flash (° F.)  520                                                      Vis. @ 300°  F. (SUS)                                                                       348                                                      Color (ASTM)         2.0                                                      C.P. (° F.)   140                                                      M.P. (° F.)   161.5                                                    Pen. @ 77°  F.                                                                              5.5                                                      Pen. @ 110°  F.                                                                             25.0                                                     ______________________________________                                    

EXAMPLE 10

600 grams of a wax with a molecular weight of 680 and an alpha olefincontent of approximately 60% was reacted with 34 grams of di-t-butylperoxide (0.262 molar ratio based on the wax) at 141° C. (286° F.) until8.0 half-lives of the peroxide had been achieved. At this point thesample was drained and stripped as in the preceding examples. Presentedbelow are properties of the charge stock and the resulting product ofthe polymerization. As can be seen, the polymerized product has a higherviscosity and greater hardness than the charge stock; however, thecongealing point and the melting point are lower. This example shows theeffect of charge stock. The use of a harder charge stock results in aharder product.

The results are presented in the following Table Example 10.

    ______________________________________                                                    Charge Stock Final Product                                        ______________________________________                                        Flash (°F.)                                                                          580                540                                          Vis. @ 300° F. (SUS)                                                                 52                 540                                          Color (ASTM)  15       (Saybolt) 0.5-                                         C.P. (°F.)                                                                           202                193                                          M.P. (°F.)                                                                           213                208.0                                        Pen. @ 77° F.                                                                        2.5                2.0                                          Pen. @ 110° F.                                                                       2.5                4.0                                          Pen. @ 140° F.                                                                       17.0               10.0                                         VPO           680                1562                                         ______________________________________                                    

EXAMPLE 11

600 grams of Gulf C₂₄₋₂₈ Alpha Olefin were mixed and reacted with 42grams of di-t-butyl peroxide (molar ratio 0.175) at 288° F. for 10.7half-lives. The polymerized product was harder and more viscous, but hada lower melting point. This example shows that by using a lowermolecular weight material the final product is softer than if a highermolecular weight starting material was used.

The results are presented in the following Table Example 11.

    ______________________________________                                                   Polymerized Product                                                                       Charge Stock                                           ______________________________________                                        Flash (°F.)                                                                         515               420                                            Color        6.0      Saybolt  16     Saybolt                                 Vis. @ 210° F. (SUS)    39                                             Vis. @ 300° F. (SUS)                                                                795                                                              C.P. (°F.)                                                                          123               126                                            M.P. (°F.)                                                                          123.5             136                                            Pen. @ 77° F.                                                                       13.0              99                                             Pen. @ 110° F.                                                                      70                Too Soft                                       ______________________________________                                    

EXAMPLE 12

1080 grams of Gulf C₃₀ + Alpha Olefin and 120 grams of the wax used inExample 10 were mixed and reacted with 87.8 grams of di-t-butyl peroxide(this has a molar ratio of 0.262). The temperature of reaction was 139°C. (282° F.). It lasted until 8.0 half-lives had been achieved. At thispoint the sample wax was drained and vacuum stripped. Shown below arethe properties of both the blend and the reacted copolymer. As can beseen the polymerized product is more viscous and is much harder thanthat of the blend. However, the blend has a higher congealing point andmelting point. From this example it can be seen that by using the properblend, the melting point and congealing point of the copolymer and theresulting product can be adjusted.

The results are presented in the following Table Example 12.

    ______________________________________                                                   Blend          Copolymer                                           ______________________________________                                        Flash (°F.)                                                                         495                  565                                         Vis. @ 300° F. (SUS)                                                                40                   472                                         Color (ASTM) 0.5-                 0.5-                                        C.P. (°F.)                                                                          176                  153                                         M.P. (°F.)                                                                          193.0                179.5                                       Pen. @ 77° F.                                                                       11.5                 2.5                                         Pen. @ 110° F.                                                                      48.0                 16.5                                        Pen. @ 140° F.                                                                      220                  98                                          VPO          523      (Calculated)                                                                              2595                                        ______________________________________                                    

4,060,569 has also determined that alpha olefins also react withhydrocarbons having no unsaturated groups. For example, alpha olefinsreact with saturated molecules such as polymers and natural or syntheticwaxes. Thus, alpha olefins can react with plastic and tank bottommicrocrystalline waxes, Fisher Tropsch waxes, ozakorite waxes, Utahwaxes, polyethylenes, polypropylenes, or other polyalkylene polymers orcopolymers, "BARECO" polywaxes, carnauba waxes, ouricury waxes,candelilla waxes, montan waxes, etc. Stated another way, the alphaolefins of this invention can also be copolymerized with saturated waxesor polymers. Although we do not wish to be bound by theoreticalconsiderations, polymerization may occur by means of hydrogenabstraction from the saturates so as to form free radicals which combinewith the alpha olefin reactants and/or products to form the reactionproducts of this invention.

The following example is presented to illustrate the reaction of alphaolefins with commercial saturated polyethylenes known as "EPOLENE"waxes. These are low molecular weight polyethylenes prepared by crackinghigh molecular weight polyethylenes, followed by hydrogenation to yieldsaturated polyethylenes.

EXAMPLE 13

540 grams of Gulf C₃₀ +Alpha Olefin and 60 grams of Eastman Epolene N-10were mixed with 30 grams of di-t-butyl peroxide. The mixture was reactedin an agitated vessel under 80 psig of nitrogen at 285° F. until 9.0half-lives had elapsed. Shown below are properties of the blend and ofthe reacted copolymer. As is consistent with the other examples, themelting point and congealing point of the blend is higher than that ofthe copolymer. However, the copolymer is more viscous and is muchharder.

The results are presented in the following Table Example 13.

    ______________________________________                                                       Blend    Copolymer                                             ______________________________________                                        Flash (°F.)                                                                             495        570                                               Color (ASTM)     0.5+       0.5-                                              Vis. @ 210° F. (SUS)                                                                    80                                                           Vis. @ 300° F. (SUS)                                                                    58         621                                               C.P. (°F.)                                                                              176        164                                               M.P. (°F.)                                                                              196        188                                               Pen. @ 77° F.                                                                           12.5       2.5                                               Pen. @ 110° F.                                                                          30.0       14.0                                              Pen @ 140° F.                                                                           185        102                                               VPO                         2075                                              ______________________________________                                    

U.S. Pat. No. 4,060,569 has also found that by following its process,saturated waxes and polymers such as described above react even in theabsence of alpha olefins to form products of this invention. Although wedo not wish to be bound by theoretical considerations, it is believedthat hydrogens are abstracted from the saturates to form free radicalswhich join a plurality of polymer molecules, thus producing a higherpolymer. The following example is presented for purposes of illustrationemploying "BARECO" polywax, which is a linear polyethylene.

EXAMPLE 14

600 grams of "BARECO" Polywax 655* and 30 grams of di-t-butyl peroxide(molar ratio=0.227) were mixed and reacted in a closed, agitated vesselwith 80 psig nitrogen pressure at 300° F. for 16 half-lives to yield aproduct having the properties shown in Table Example 14 below. There wasa reaction, but not to the extent of that when using alpha olefins. Thisexample shows that saturates do react in a manner consistent with theother examples to yield a product having lower congealing and meltingpoints and higher viscosity.

Table Example 14.

    ______________________________________                                                       Charge Stock                                                                           Reaction Product                                      ______________________________________                                        Flash (° F.)                                                                            565        580                                               Vis. @300°  F. (SUS)                                                                    49         60                                                Color (ASTM)     .5-        1.-                                               C.P. (° F.)                                                                             205        200                                               M.P. (° F.)                                                                             216        214.5                                             Pen. @ 77°  F.                                                                          2.0        1.0                                               Pen. @ 110°  F.                                                                         4.0        5.0                                               Pen. @@ 140  F.  12.0       16.0                                              Molecular Weight (by VPO)                                                                      664        787                                               ______________________________________                                    

EXAMPLE 15

100 parts of Gulf C₃₀ +Alpha Olefin and 5 parts t-butyl perbenzoate(molar ratio equal to 0.130) were reacted at 120° C. for three hours inan oven with a nitrogen purge. No pressure was employed in this example.The sample was then vacuum stripped for two hours at 120° C. to removethe decomposition products (benzoic acid and t-butyl alcohol). Shownbelow are the results of this example. The purpose of this example is toshow that peroxides other than di-t-butyl peroxide can be usedsuccessfully.

The results are presented in the following Table Example 15.

    ______________________________________                                        Flash(°F.) 485                                                         Vis. @ 210° F. (SUS)                                                                     226                                                         Vis. @ 300° F. (SUS)                                                                      91                                                         C.P. (°F.) 154                                                         M.P. (°F.) 172.5                                                       Pen. @ 77° F.                                                                             7.0                                                        Pen. @ 110° F.                                                                            48                                                         Pen. @ 140° F.                                                                           Too Soft                                                    Color              0.5+(Murky)                                                ______________________________________                                    

EXAMPLE 16

2,000 grams of Gulf C₃₀ +Alpha Olefin and 60 grams of Lupersol 70 (75%t-butyl peracetate (molar ratio 0.088) and 25% C-12 solvent) werereacted in an agitated vessel under 100 psig of nitrogen at 130° C.After 12 half-lives the sample was drained and the decompositionproducts and the mineral oil (peroxide diluent) were vacuum strippedfrom the resulting wax.

The results are presented in the following Table Example 16.

    ______________________________________                                        Flash (°F.)   480                                                      Vis. @ 210° F. (SUS)                                                                        99                                                       Vis. @ 300° F. (SUS)                                                                        54                                                       Color (ASTM)         0.5-                                                     C.P. (°F.)    155                                                      M.P. (°F.)    172.5                                                    Pen. @ 77° F. 5.0                                                      Pen. @ 110° F.                                                                              33.5                                                     ______________________________________                                    

EXAMPLE 17

In the above examples, the reactions are always vacuum stripped. Thereason for this is that the decomposition products of the peroxide havea deleterious effect upon the polymerized product. Shown below areresults of a sample of wax from Example 16 that was not vacuum stripped.As can be seen, the unstripped sample has a lower melting point and ahigher penetration.

The results are presented in the following Table Example 17.

    ______________________________________                                        Flash (°F.)   510                                                      Vis. @ 210° F. (SUS)                                                                        86                                                       Vis. @ 300° F. (SUS)                                                                        54                                                       Color (ASTM)         0.5-                                                     C.P. (°F.)    154                                                      M.P. (°F.)    166.7                                                    Pen. @ 77° F. 7.5                                                      Pen. @ 110° F.                                                                              36.0                                                     ______________________________________                                    

EXAMPLE 18

The polymerized product can be oxidized to form a wax that is suitablefor floor polishes and emulsions. A product similar to that of Example 3was oxidized at 250° F. for 25 hours. Shown below are the products ofthis oxidation and the charge stock before oxidation.

The results are presented in the following Table Example 18.

    ______________________________________                                                      Charge Stock                                                                            Oxidized Product                                      ______________________________________                                        Flash (°F.)                                                                            560         520                                               Viscosity @ 300° F. (SUS)                                                              623         666                                               Color (ASTM)    0.5+        1.5-                                              C.P. (°F.)                                                                             140         140                                               M.P. (°F.)                                                                             165.0       159.0                                             Pen. @ 77° F.                                                                          4.5         4.5                                               Pen. @ 110° F.                                                                         22.0        23.5                                              Acid No.        Nil         16.3                                              Sap. No.        Nil         33.88                                             ______________________________________                                    

EXAMPLE 19

To show the homogeneity of the polymerized wax the polymerized productwas subjected to fractionation in methyl isobutyl ketone. Twoextractions were done on the material produced in Example 3, one at 80°F. and one at 100° F. Both used a solvent to wax ratio of nine to one.The results of these extractions are listed below. The amount of waxextracted at 80° F. was far less than that extracted at 100° F. Fromthis data it can be seen that there is a small amount of low molecularweight and low melting point material. However, most of the material hasa congealing point, melting point, and penetration approximately thesame as that of the polymerized product. This shows that thepolymerization product is not a simple blend. If it was a blend then thefiltrate would contain much more of the material and the cake would beof much higher congealing point, melting point, and hardness.

The results are presented in the following Table Example 19.

    ______________________________________                                        Temperature of Extraction                                                                        80° F.                                                                            100° F.                                  ______________________________________                                        Cake:     Yield        91.0%      80.1%                                                 C.P. (°F.)                                                                          149        150                                                   M.P. (°F.)                                                                          162        162.2                                                 Pen. @ 77° F.                                                                       3.0        3.0                                         Filtrate: Yield        9.0%       19.9%                                                 C.P. (°F.)                                                                          120        132                                                   M.P. (°F.)                                                                          124.5      146                                                   Pen. @ 77° F.    28.5                                        ______________________________________                                    

In summary, U.S. Pat. No. 4,060,569 relates to a process of preparing apolymer which comprises reacting

(1) a hydrocarbon, but preferably an olefin, and most preferably analpha olefin, (for example vinyl or vinylidene) alone or as copolymers

(2) under free radical conditions (for example, in the presence ofperoxides)

(3) at pressures which are sufficient to keep the peroxides andreactants from vaporizing (for example, under 500 psi but preferablyunder 150 psi) so as to yield polymer products having the followingproperties:

(a) higher molecular weight

(b) higher viscosities

(c) greater hardness and

(d) lower penetration

but having a

(e) congealing point and melting point which are essentially no higherthan the starting alpha olefin containing material.

This invention also includes the polymerization of saturatedhydrocarbons either alone or in combination with alpha olefins.

Although alpha olefins are preferred, U.S. Pat. No. 4,060,569 alsoincludes the polymerization of olefins which are not alpha olefins.

The above section described the hydrocarbon polymers of U.S. Pat. No.4,060,569.

The following are examples of commercial hydrocarbon polymers which canbe employed in this invention. They are prepared from a C₃₀ +α-olefin.

                                      TABLE 2                                     __________________________________________________________________________    Typical Properties                                                            Property   Test Method                                                                             Units   *VYBAR® 260                                                                     *VYBAR® 103                            __________________________________________________________________________    Molecular Wgt.               2600    2830                                     Melting Point                                                                            ASTM D-36 Mod.                                                                          °F. (°C.)                                                               124(51) 162(72)                                  Pour Point ASTM D-97 °F. (°C.)                                                               N/A     N/A                                      Viscosity                                                                      @ 32° F. (0° C.)                                                          ASTM D-2669                                                                             Centipoise                                                                            --      --                                        @ 50° F. (10° C.)                                               @ 100° F. (37.8° C.)                                                      ASTM D-3236       --      --                                        @ 150° F. (65.6° C.)                                                                        915     --                                        @ 210° F. (98.9° C.)                                                                        350     360                                       @ 250° F. (121° C.)                                                                         180     185                                       @ 300° F. (149° C.)                                                                         104     107                                      Penetration                                                                    @ 77° F. (25° C.)                                                         ASTM D-1321                                                                             0.1 mm  13      5                                         @ 110° F. (43° C.)                                                                          110     20                                        @ 130° F. (54° C.)                                                                          --      57                                        @  140° F. (60° C.)                                                                         --      153                                      Density                                                                        @ 75° F. (24° C.)                                                         ASTM D-1168                                                                             grams/cc                                                                              0.90    0.92                                      @ 200° F. (93° C.)                                                                          0.79    0.77                                     Iodine Number                                                                            ASTM D-1959                                                                             ogI.sub.2 /g sample                                                                   15      14                                       Color      ASTM D-1500       0.5     0.5                                      __________________________________________________________________________     N/A Not Applicable                                                            *Registered Trademark, Petrolite Corp., marketed by Bareco Division.     

The blends can be prepared by any suitable means. In practice they areprepared by melting the wax and the hydrocarbon polymer in the desiredproportions and stirring the melted compounds to get a homogenous blend.They are in essence physical blends.

The following examples are presented for purposes of illustration andnot of limitation.

                                      TABLE 3                                     __________________________________________________________________________    VYBAR® 103 as as Additive to Oily Paraffins to Improve Their Oil          Retention Properties                                                          Wgt % VYBAR® 103                                                                         0%   2% 3%  4%  5% 7.5%                                                                             10% 15%                                                                              20%                                                                              50%                            __________________________________________________________________________    Paraffin                                                                      Melt Point 141° F., 2.16% Oil                                          24 hrs @ 107° F.                                                       Area cm.sup.2  --   -- --  --  -- -- --  -- -- --                             % of bleed     90   nil                                                                              nil nil nil                                                                              nil                                                                              --  -- -- --                             Melt Point, 140° F., 9-10% Oil                                         24 hrs. @ 107° F.                                                      Area cm.sup.2  227  165                                                                              83.6                                                                              39.8                                                                              -- -- --  -- -- --                             % of bleed     1292 940                                                                              476 227 50  5 --  -- -- --                             Melt Point 100° F., 30% Oil                                            24 hrs. @ 90° F.                                                       Area cm.sup.2  706.5                                                                              --  -- --  143                                                                              -- 103.4                                                                             -- -- --                             % of bleed     4000+                                                                              -- --  --  815                                                                              -- 591 60 5  nil                            Melt Point 141° F., 2.16% Oil                                          24 hrs. @ 120° F.                                                      Area cm.sup.2  28.3 -- --  --  -- -- --  -- -- --                             % of bleed     161   95                                                                              95  80  80 60 --  -- -- --                             __________________________________________________________________________     Samples are prepared by pouring 20 grams of molten wax into a standard        aluminum weighting dish. The samples are allowed to solidify and are then     removed from the dishes. They are then placed on cardboard, which has bee     covered with kraft paper. The test runs for 24 hrs. at whatever the           desired temperature is.                                                       Oil stain (bleed) is read as the % of the original wax surface in contact     with the kraft paper which shows staining by the oil.                    

The amounts of hydrocarbon polymers employed in oils will vary widelydepending on the particular oil, the particular hydrocarbon polymer, theparticular properties desired in the gel or paste, etc. In general,higher percentages are employed in oils as compared to solid waxes.Thus, from about 0.5 to 99% by weight hydrocarbon polymer can beemployed in the oils, such as from about 5-90%, for example from about10-70%, but preferably from about 30-60%.

The following examples are presented for purposes of illustration andnot of limitation.

                  TABLE 4                                                         ______________________________________                                        VYBAR® 103 and 260 in paraffinic oil and naphthenic oil.                  Percent (%) is by weight.                                                     VYBAR®/mineral oil mixtures were heated in an oven to 225° F.      and cooled with hand stirring to 5° F. above the solidifica-           tion point. Specimens were aged for 14 hours at room                          temperature and cone penetration at 77° F. was taken                   (ASTM D-938/15 g cone).                                                       ______________________________________                                        % VYBAR® 260                                                                          % Paraffinic Oil                                                                            Penetration Values                                  ______________________________________                                        50          50            17.5                                                40          60            30                                                  30          70            53                                                  20          80            127                                                 10          90            336                                                 VYBAR® 103                                                                            Paraffinic Oil                                                                              Penetration Values                                  ______________________________________                                        50          50            9                                                   40          60            11                                                  30          70            24                                                  20          80            64                                                  10          90            170                                                 VYBAR® 260                                                                            Naphthenic Oil                                                                              Penetration Values                                  ______________________________________                                        50          50            20                                                  40          60            30                                                  30          70            52                                                  20          80            107                                                 10          90            335                                                 VYBAR® 103                                                                            Naphthenic Oil                                                                              Penetration Values                                  ______________________________________                                        50          50            8                                                   40          60            12                                                  30          70            23                                                  20          80            65                                                  10          90            220                                                 ______________________________________                                    

By means of this invention oils can be upgraded to, and used as a wax orwaxy paste in any suitable application such as a polish, etc.

While certain representative embodiments have been shown for purposes ofillustration, various modifications can be made without departing fromthe spirit and scope of the invention.

We claim:
 1. An oil-containing wax characterized by the presence ofsufficient hydrocarbon polymer to inhibit the exudation of the oil tothe surface of the wax, said hydrocarbon polymer having congealing andmelting points which are essentially no higher than those of itsstarting materials, said hydrocarbon polymer prepared by polymerizing ahydrocarbon starting material consisting primarily of alpha olefins andwhich is a solid at room temperature, in the presence of a source offree radicals under pressure of less than 500 psi but sufficient to keepthe reactants from vaporizing and at a temperature of about 40° to 250°C.
 2. The product of claim 1 where the oil-containing wax is a naturalwax or a petroleum hydrocarbon wax.
 3. The product of claim 2 where thehydrocarbon polymer is prepared by polymerizing an alpha olefin fractionhaving mostly C₃₀ and higher in the presence of a peroxide orhydroperoxide free radical forming catalyst under said pressure and atsaid temperature.
 4. The product of claim 3 where the oil-containing wasis a paraffin wax with an oil content of at least 0.5%.
 5. The productof claim 3 where the oil-containing wax is a microcrystalline wax.
 6. Anoil characterized by the presence of sufficient hydrocarbon polymer tothicken said oil, said hydrocarbon polymer having congealing and meltingpoints which are essentially no higher than those of its startingmaterials, said hydrocarbon polymer prepared by polymerizing ahydrocarbon starting material consisting primarily of alpha olefins andwhich is a solid at room temperature, in the presence of a source offree radicals under pressure of less than 500 psi but sufficient to keepthe reactants from vaporizing and at a temperature of about 40° to 250°C.
 7. The product of claim 6 where the oil is an animal oil.
 8. Theproduct of claim 6 where the oil is a vegetable oil.
 9. The product ofclaim 6 where the oil is a petroleum oil.
 10. The product of claim 9where the hydrocarbon polymer is prepared by polymerizing an alphaolefin fraction having mostly C₃₀ and higher in the presence of aperoxide or hydroperoxide free radical forming catalyst under saidpressure and at said temperature .
 11. The product of claim 10 where theoil is a paraffinic or naphthenic oil.